Resin composition

ABSTRACT

A resin composition is provided. The resin composition includes a polyimide resin; a hydrocarbon resin or a fluorinated polymer resin; and a silica that is modified by a surface modifier. The content of the hydrocarbon resin is in a range from 1 to 13 parts by weight based on 100 parts by weight of the polyimide resin. The content of the fluorinated polymer resin is in a range from 1 to 60 parts by weight based on 100 parts by weight of the polyimide resin. The content of the silica is in a range from 1 to 10 parts by weight based on 100 parts by weight of the polyimide resin.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority of provisional U.S. Application No.62/594,693, filed on Dec. 5, 2017, the entirety of which is incorporatedby reference herein.

TECHNICAL FIELD

The present disclosure relates to a resin composition, and in particularit relates to a polyimide (PI) resin composition.

BACKGROUND

As the information society develops rapidly, demands on the quality andspeed of information transmission are becoming more and morerestrictive. High-frequency and high-speed signal transmission is thecurrent developmental trend, and the development of materials used inhigh-frequency communication is also gradually gaining attention. Forexample, substrate materials for devices that are equipped with signaltransmission function (e.g., mobile phones, routers, servers, computers,etc.) are being improved to have low signal transmission loss so thatthe substrate can be made suitable for the transmission ofhigh-frequency signals.

The dielectric constant (Dk) and the dielectric loss factor (Df) ofmaterials are important indicators that affect the speed and quality ofsignal transmission. Substrate materials having a low dielectricconstant and a low dielectric loss factor can prevent the signal loss oftransmission. The speed of high-frequency transmission and the integrityof the signal can also be maintained.

Polyimide resins possess good stability, heat resistance, coefficient ofthermal expansion, mechanical strength, electrical resistance, and soon, and they are commonly used in the fabrication of flexible substrates(e.g., printed circuit boards (PCBs)). However, the dielectric lossfactor of the polyimide resin is increased drastically in high-frequencyenvironments, and the speed and quality of signal transmission in thedevice will be affected.

As described above, although existing materials used in communicationdevices have been adequate for their intended purposes, they have notbeen entirely satisfactory in all respects. In order to comply with thedemands for high-frequency and high-speed signal transmission, thematerials that can maintain a low loss of signal transmission in ahigh-frequency environment are expected in the industry.

SUMMARY

In accordance with some embodiments of the present disclosure, a resincomposition is provided. The resin composition comprises a polyimideresin; a hydrocarbon resin; and a silica that is modified by a surfacemodifier. The content of the hydrocarbon resin is in a range from 1 to13 parts by weight based on 100 parts by weight of the polyimide resin,and the content of the silica is in a range from 1 to 10 parts by weightbased on 100 parts by weight of the polyimide resin.

In accordance with some embodiments of the present disclosure, a resincomposition is provided. The resin composition comprises a polyimideresin; a fluorinated polymer resin; and a silica that is modified by asurface modifier. The content of the fluorinated polymer resin is in arange from 1 to 60 parts by weight based on 100 parts by weight of thepolyimide resin, and the content of the silica is in a range from 1 to10 parts by weight based on 100 parts by weight of the polyimide resin.

DETAILED DESCRIPTION

The resin composition and the method for manufacturing the resincomposition provided by the present disclosure are described in detailin the following description. In the following description, for purposesof explanation, numerous specific details and examples or embodimentsare set forth in order to provide a thorough understanding of thepresent disclosure. It will be apparent, however, that the exemplaryembodiments set forth herein are used merely for the purpose ofillustration, and the concept of the present disclosure may be embodiedin various forms without being limited to those exemplary embodiments.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. It should be appreciated that,in each case, the term, which is defined in a commonly used dictionary,should be interpreted as having a meaning that conforms to the relativeskills of the present disclosure and the background or the context ofthe present disclosure, and should not be interpreted in an idealized oroverly formal manner unless so defined.

In accordance with some embodiments of the present disclosure, the resincomposition is provided. The resin composition includes polyimide resinand fluorinated polymer resin or hydrocarbon resin. The fluorinatedpolymer resin and the hydrocarbon resin are added so that the resincomposition can still maintain good dielectric properties in ahigh-frequency environment and the loss of signal transmission can beeffectively decreased. Therefore, when the elements made of such resincomposition (for example, a substrate, a printed circuit board, or thelike) are applied to a signal transmission device, the rate ofhigh-frequency transmission and the integrity of the transmission signalof the device can be effectively improved.

In addition, based on the specific component and ratio of the resincomposition, the dielectric loss factor of the cured resin compositionmay be maintained below 0.007 in a high-frequency environment inaccordance with some embodiments of the present disclosure. The curedresin composition may also possess low water absorption rate (e.g., lessthan 1%) and low coefficient of thermal expansion (CTE).

In accordance with some embodiments of the present disclosure, the resincomposition includes a polyimide resin, a hydrocarbon resin and a silicathat is modified by a surface modifier (i.e. surface modified silica).In accordance with some embodiments of the present disclosure, thecontent of the hydrocarbon resin is in a range from about 1 to about 13parts by weight based on 100 parts by weight of the polyimide resin. Inaccordance with some embodiments of the present disclosure, the contentof the silica (silicon dioxide) that is modified by the surface modifieris in a range from about 1 to about 10 parts by weight based on 100parts by weight of the polyimide resin. For example, in accordance withsome embodiments of the present disclosure, based on 100 parts by weightof the polyimide resin, the content of the silica that is modified bythe surface modifier is in a range from about 2 to about 7 parts byweight, or from about 3 to about 6 parts by weight.

In accordance with some embodiments of the present disclosure, thepolyimide resin is obtained by copolymerizing the following components(a) at least two dianhydride monomers and (b) at least two diaminemonomers. In accordance with some embodiments of the present disclosure,one of the (a) at least two dianhydride monomers isp-phenylenebis(trimellitate anhydride) and its content accounts forabout 80% to about 95% of the total moles of the dianhydride monomers.In addition, the other (or another) dianhydride monomers of the (a) atleast two dianhydride monomers (i.e. the dianhydride monomers other thanp-phenylenebis(trimellitate anhydride)) are selected from a groupconsisting of 4,4′-(hexafluoroisopropylidene)-diphthalic anhydride, and4,4′-(4,4′-isopropyldiphenoxy)bis(phthalic anhydride). In accordancewith some embodiments of the present disclosure, one of the (b) at leasttwo diamine monomers is 2,2′-bis(trifluoromethyl)benzidine and itscontent accounts for about 70% to about 90% of total moles of thediamine monomers. In addition, the other (or another) diamine monomersof the (b) at least two diamine monomers (i.e. the diamine monomersother than 2,2′-bis(trifluoromethyl)benzidine) are selected from a groupconsisting of 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane,2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4′-diaminodiphenyl-sulfone,1,3-bis(4-aminophenoxy)benzene, 4,4′-diaminobenzanilide,p-phenylenediamine, 4,4′-diamino-2,2′-dimethyl-1,1′-biphenyl,2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and4,4′-diamino octafluorobiphenyl,2,2-bis(3-amino-4-tolyl)hexafluoropropane, and2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and its contentaccounts for about 10% to about 30% of the total moles of the diaminemonomers. Moreover, in accordance with some embodiments of the presentdisclosure, the ratio of total moles of dianhydride monomers to totalmoles of diamine monomers is in a range from about 0.85 to about 1.15.

In accordance with some embodiments of the present disclosure, thedianhydride monomers and/or the diamine monomers that are used to formthe polyimide resin include the fluorine-containing monomer. In otherwords, the polyimide resin contains fluorine in accordance with someembodiments of the present disclosure. In accordance with someembodiments of the present disclosure, the dianhydride monomers that areused to form the polyimide resin includes4,4′-(hexafluoroisopropylidene)bis-phthalic anhydride and its contentaccount for not more than 15% (at most 15%) of the total moles of thedianhydride monomers. In accordance with some embodiments of the presentdisclosure, the diamine monomers that are used to form the polyimideresin includes2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,4,4′-diamino octafluorobiphenyl,2,2-bis(3-amino-4-tolyl)hexafluoropropane,2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, or a combinationthereof, and its content account for about 10% to about 30% of the totalmoles of the diamine monomers. In addition, the polyimide resin may bethermoplastic resin in accordance with some embodiments of the presentdisclosure.

In accordance with some embodiments of the present disclosure, thehydrocarbon resin includes polybutadiene, polybutadiene-styrene mixture,polyisoprene, cyclic olefin copolymer, butadiene-styrene-divinylbenzenecopolymer, or a combination thereof. In accordance with some embodimentsof the present disclosure, the number-average molecular weight (Mn) ofthe hydrocarbon resin is in a range from about 1000 to about 9000, fromabout 1000 to about 5000, from about 1000 to about 3000, or from about1000 to about 2000. As described above, the resin composition includesabout 1 to about 13 parts by weight of the hydrocarbon resin (based on100 parts by weight of the polyimide resin). In particular, the resincomposition in which the hydrocarbon resin is added may maintain gooddielectric properties in a high-frequency environment and mayeffectively reduce the loss of signal transmission.

In accordance with some embodiments of the present disclosure, thesilica (silicon dioxide) may serve as filler to further control thecoefficient of thermal expansion (CTE) of the resin composition. Inaccordance with some embodiments of the present disclosure, a volumemean diameter (a volume-based average particle size) of the silica is ina range from about 0.5 μm to about 25 μm. For example, in accordancewith some embodiments of the present disclosure, the volume meandiameter of the silica is in a range from about 2 μm to about 15 μm, orfrom about 3 μm to about 11 μm. It should be noted that if the particlesize of the silica is too large (e.g., larger than 25 μm), it may bedifficult for the silica to disperse in the resin composition so thatthe difficulty of the mixing step may be increased; on the other hand,if the particle size of the silica is too small (e.g., smaller than 0.5μm), then the resin composition may be easily broken after thecyclization process of the polyimide resin.

As described above, the silica may be modified by the surface modifier.The silica that has been modified by the surface modifier (i.e. surfacemodified silica) does not affect the dielectric loss factor of the resincomposition. In accordance with some embodiments of the presentdisclosure, the content of the surface modifier that is used to modifythe silica is in a range from about 0.1 to about 5 parts by weight basedon 100 parts by weight of the silica. In accordance with someembodiments of the present disclosure, the surface modifier includesvinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane,isobutyltrimethoxysilane, isobutyltriethoxysilane,octyltrimethoxysilane, octyltriethoxysilane, octadecyltrimethoxysilane,octadecylethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane,3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminoethylaminopropyl trimethoxysilane, aminoethyl aminopropyl triethoxysilane,3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane,or a combination thereof.

In accordance with some embodiments of the present disclosure, thedielectric loss factor of the cured product of the above resincomposition is less than about 0.007 under high-frequency conditions.For example, the dielectric loss factor of the cured resin compositionmay be less than about 0.006, less than about 0.005, less than about0.004, or less than about 0.003 in accordance with some embodiments.Moreover, in accordance with some embodiments of the present disclosure,the linear coefficient of thermal expansion the cured product of theabove resin composition is in a range from about 15 to about 50 ppm/K,for example, from about 15 to about 35 ppm/K. In accordance with someembodiments of the present disclosure, the high-frequency section is ina range of greater than about 10 GHz, for example, greater than about 20GHz, or greater than about 30 GHz.

Furthermore, in accordance with some embodiments of the presentdisclosure, the curing process of the resin composition can be carriedout by applying a mixture of the resin composition onto a copper foiland heating. Specifically, the temperature of the curing process may bein a range from about 100° C. to about 200° C., for example, from about120° C. to about 150° C. After the curing process of the resincomposition, the cyclization process of the polyimide resin can beperformed. In accordance with some embodiments of the presentdisclosure, the temperature of the cyclization process may be in a rangefrom about 250° C. to about 450° C., for example, from about 350° C. toabout 400° C.

In accordance with some other embodiments of the present disclosure, aresin composition is provided. The resin composition includes apolyimide resin, a fluorinated polymer resin and a silica that ismodified by a surface modifier. In accordance with some embodiments ofthe present disclosure, the content of the fluorinated polymer resin isin a range from about 1 to about 60 parts by weight based on 100 partsby weight of the polyimide resin. For example, in accordance with someembodiments of the present disclosure, based on 100 parts by weight ofthe polyimide resin, the content of the fluorinated polymer resin is ina range from about 5 to about 50 parts by weight, from about 10 to about40 parts by weight, or from about 30 to about 40 parts by weight. Inaccordance with some embodiments of the present disclosure, the contentof the silica that is modified by surface modifier is in a range fromabout 1 to about 10 parts by weight based on 100 parts by weight of thepolyimide resin. For example, in accordance with some embodiments of thepresent disclosure, based on 100 parts by weight of the polyimide resin,the content of the silica that is modified by the surface modifier is ina range from about 2 to about 7 parts by weight, or from about 3 toabout 5 parts by weight.

In accordance with some embodiments of the present disclosure, thepolyimide resin is obtained by copolymerizing the following components(a) at least two dianhydride monomers and (b) at least two diaminemonomers. In accordance with some embodiments of the present disclosure,one of the (a) at least two dianhydride monomers isp-phenylenebis(trimellitate anhydride) and its content accounts forabout 80% to about 95% of the total moles of the dianhydride monomers.In addition, the other (or another) dianhydride monomers of the (a) atleast two dianhydride monomers (i.e. the dianhydride monomers other thanp-phenylenebis(trimellitate anhydride)) are selected from a groupconsisting of 4,4′-(hexafluoroisopropylidene)-diphthalic anhydride, and4,4′-(4,4′-isopropyldiphenoxy)bis(phthalic anhydride). In accordancewith some embodiments of the present disclosure, one of the (b) at leasttwo diamine monomers is 2,2′-bis(trifluoromethyl)benzidine and itscontent accounts for about 70% to about 90% of total moles of thediamine monomers. In addition, the other (or another) diamine monomersof the (b) at least two diamine monomers (i.e. the diamine monomersother than 2,2′-bis(trifluoromethyl)benzidine) are selected from a groupconsisting of 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane,2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4′-diaminodiphenyl-sulfone,1,3-bis(4-aminophenoxy)benzene, 4,4′-diaminobenzanilide,p-phenylenediamine, 4,4′-diamino-2,2′-dimethyl-1,1′-biphenyl,2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and4,4′-diamino octafluorobiphenyl,2,2-bis(3-amino-4-tolyl)hexafluoropropane, and2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and its contentaccounts for about 10% to about 30% of the total moles of the diaminemonomers. Moreover, in accordance with some embodiments of the presentdisclosure, the ratio of the total moles of dianhydride monomers to thetotal moles of diamine monomers is in a range from about 0.85 to about1.15.

In accordance with some embodiments of the present disclosure, thedianhydride monomers and/or the diamine monomers that are used to formthe polyimide resin include the fluorine-containing monomer. In otherwords, the polyimide resin contains fluorine in accordance with someembodiments of the present disclosure. In accordance with someembodiments of the present disclosure, the dianhydride monomers that areused to form the polyimide resin includes4,4′-(hexafluoroisopropylidene)bis-phthalic anhydride and its contentaccounts for not more than 15% of the total moles of the dianhydridemonomers. In accordance with some embodiments of the present disclosure,the diamine monomers that are used to form the polyimide resin includes2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,4,4′-diamino octafluorobiphenyl,2,2-bis(3-amino-4-tolyl)hexafluoropropane,2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, or a combinationthereof, and its content accounts for about 10% to about 30% of thetotal moles of the diamine monomers. In accordance with some embodimentsof the present disclosure, the fluorinated polymer resin includespolytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP),soluble polytetrafluoroethylene (perfluoroalkoxy alkane, PFA), copolymerof tetrafluoroethylene and perfluoromethyl-vinylether (MFA), or acombination thereof.

In accordance with some embodiments of the present disclosure, thevolume mean diameter of the fluorinated polymer resin is less than about20 μm. For example, in accordance with some embodiments of the presentdisclosure, the volume mean diameter of the fluorinated polymer resin isin a range from about 2 μm to about 20 μm, from about 3 μm to about 10μm, or from about 3 μm to about 5 μm. As described above, in accordancewith some embodiments of the present disclosure, the resin compositionincludes about 1 to about 60 parts by weight of the fluorinated polymerresin (based on 100 parts by weight of the polyimide resin). Inparticular, the resin composition in which the fluorinated polymer resinis added may maintain good dielectric properties in a high-frequencyenvironment and may effectively reduce the loss of signal transmission.

In accordance with some embodiments of the present disclosure, thesilica (silicon dioxide) may serve as filler to further control thecoefficient of thermal expansion (CTE) of the resin composition. Inaccordance with some embodiments of the present disclosure, a volumemean diameter of the silica is in a range from about 0.5 μm to about 25μm. For example, in accordance with some embodiments of the presentdisclosure, the volume mean diameter of the silica is in a range fromabout 2 μm to about 15 μm, or from about 3 μm to about 11 μm. It shouldbe noted that if the particle size of the silica is too large (e.g.,larger than 25 μm), it may be difficult for the silica to disperse inthe resin composition so that the difficulty of the mixing step may beincreased; on the other hand, if the particle size of the silica is toosmall (e.g., smaller than 0.5 μm), then the resin composition may beeasily broken after the cyclization process of the polyimide resin. Inaddition, in accordance with some embodiments of the present disclosure,the ratio of the particle size of the fluorinated polymer resin to thesilica is in a range from about 0.1 to about 40. For example, the ratioof the particle size of the fluorinated polymer resin to the silica maybe in a range from about 0.1 to about 20, or from about 0.2 to about 2.

As described above, the silica may be modified by the surface modifier.The silica that has been modified by the surface modifier (i.e. surfacemodified silica) does not affect the dielectric loss factor of the resincomposition. In accordance with some embodiments of the presentdisclosure, the content of the surface modifier that is used to modifythe silica is in a range from about 0.1 to about 5 parts by weight basedon 100 parts by weight of the silica. In accordance with someembodiments of the present disclosure, the surface modifier includesvinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane,isobutyltrimethoxysilane, isobutyltriethoxysilane,octyltrimethoxysilane, octyltriethoxysilane, octadecyltrimethoxysilane,octadecylethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane,3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminoethylaminopropyl trimethoxysilane, aminoethyl aminopropyl triethoxysilane,3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane,or a combination thereof.

In accordance with some embodiments of the present disclosure, thedielectric loss factor of the cured product of the above resincomposition is less than about 0.007 under high-frequency (larger than10 GHz, e.g., larger than 20 GHz or larger than 30 GHz) conditions. Forexample, the dielectric loss factor of the cured resin composition maybe less than about 0.006, less than about 0.005, less than about 0.004,or less than about 0.003 in accordance with some embodiments. Moreover,in accordance with some embodiments of the present disclosure, thelinear coefficient of thermal expansion the cured product of the aboveresin composition is in a range from about 15 to about 50 ppm/K.

A detailed description is given in the following particular embodimentsin order to provide a thorough understanding of the present disclosure.However, the scope of the present disclosure is not intended to belimited to the particular embodiments. Furthermore, in the examples andcomparative examples, the measurement methods regarding the variousproperties of the resin composition are also explained as follows.

Example 1: Resin Composition A1

(1) Surface Modification of Silica (SiO₂)

20 g of SiO₂ (the volume mean diameter is 2-3 μm) and 0.2 g ofvinyltriethoxysilane (which was bought from Shin-Etsu, catalogue numberKBE-1003) were dispersed in 10 g of water (pH=3.5), and were stirred for20 minutes and dried at 120° C.

(2) Preparation of Polyimide Resin Solution (Precursor of PolyimideResin)

24.20 g (0.076 moles) of 2,2′-bis(trifluoromethyl)benzidine (TFMB), 1.85g (0.017 moles) of p-phenylenediamine (PDA), 2.36 g (0.008 moles) of1,3-bis(4-aminophenoxy)benzene (TPE-R) and 244.37 g ofN-methyl-2-pyrrolidone (NMP) were placed in a three-necked bottle. Aftercomplete dissolution with stirring at 30° C., 41.75 g (0.091 moles) ofp-phenylenebis(trimellitate anhydride) (TAHQ) and 2.83 g (0.005 moles)of 4,4′-(4,4′-isopropyldiphenoxy)bis(phthalic anhydride) (PBADA) wereadded to the above mixture. Then, the mixture was stirred continuouslyand reacted at 25° C. for 24 hours to obtain the polyimide resinsolution.

(3) Preparation of Mixture of Resin Composition A1

25 g of butanone was added to 10 g of polybutadiene (the number-averagemolecular weight=1500) (which was bought from Polysciences, Inc.,catalogue number 22395) and 2.2 g oftetramethyltetravinylcyclotetrasiloxane (which was bought from AlfaAesar, catalogue number T22A066) to form a mixture of polybutadieneresin. Then, 6.5 g of the above mixture of polybutadiene resin was addedto 50 g of the above polyimide resin solution and 2.5 g of the abovesurface modified SiO₂ to form a mixture of resin composition A1.

(4) Preparation of Cured Product of Resin Composition A1

A three-wheel roller (400 rpm) was used to uniformly disperse the abovemixture of resin composition A1, and then the mixture was subjected to avacuum defoaming process. Then, the mixture of resin composition A1 wascoated on a copper foil and dried at 140° C. for 6 minutes to carry outthe curing process. Then, the mixture of resin composition A1 was heatedat 380° C. for 10 minutes to carry out a cyclization (imidation)process. Then, the copper foil was removed to obtain a cured film of theresin composition A1, and the thickness of the cured film was measured.

Example 2: Resin Composition A2

(1) Surface Modification of Silica (SiO₂)

20 g of SiO₂ (the volume mean diameter is 2-3 μm) and 0.2 g ofvinyltriethoxysilane (which was bought from Shin-Etsu, catalogue numberKBE-1003) were dispersed in 10 g of water (pH=3.5), and were stirred for20 minutes and dried at 120° C.

(2) Preparation of Polyimide Resin Solution (Precursor of PolyimideResin)

24.20 g (0.076 moles) of 2,2′-bis(trifluoromethyl)benzidine (TFMB), 1.85g (0.017 moles) of p-phenylenediamine (PDA), 2.36 g (0.008 moles) of1,3-bis(4-aminophenoxy)benzene (TPE-R) and 244.37 g ofN-methyl-2-pyrrolidone (NMP) were placed in a three-necked bottle. Aftercomplete dissolution with stirring at 30° C., 41.75 g (0.091 moles) ofp-phenylenebis(trimellitate anhydride) (TAHQ) and 2.83 g (0.005 moles)of 4,4′-(4,4′-isopropyldiphenoxy)bis(phthalic anhydride) (PBADA) wereadded to the above mixture. Then, the mixture was stirred continuouslyand reacted at 25° C. for 24 hours to obtain the polyimide resinsolution.

(3) Preparation of Mixture of Resin Composition A2

25 g of butanone was added to 10 g of polybutadiene (the number-averagemolecular weight=3000) (which was bought from Polysciences, Inc.,catalogue number 06081) and 2.2 g oftetramethyltetravinylcyclotetrasiloxane (which was bought from AlfaAesar, catalogue number T22A066) to form a mixture of polybutadieneresin. Then, 6.5 g of the above mixture of polybutadiene resin was addedto 50 g of the above polyimide resin solution and 2.5 g of the abovesurface modified SiO₂ to form a mixture of resin composition A2.

(4) Preparation of Cured Product of Resin Composition A2

A three-wheel roller (400 rpm) was used to uniformly disperse the abovemixture of resin composition A2, and then the mixture was subjected to avacuum defoaming process. Then, the mixture of resin composition A2 wascoated on a copper foil and dried at 140° C. for 6 minutes to carry outthe curing process. Then, the mixture of resin composition A2 was heatedat 380° C. for 10 minutes to carry out a cyclization (imidation)process. Then, the copper foil was removed to obtain a cured film of theresin composition A2, and the thickness of the cured film was measured.

Example 3: Resin Composition A3

(1) Surface Modification of Silica (SiO₂)

20 g of SiO₂ (the volume mean diameter is 2-3 μm) and 0.2 g ofvinyltriethoxysilane (which was bought from Shin-Etsu, catalogue numberKBE-1003) were dispersed in 10 g of water (pH=3.5), and were stirred for20 minutes and dried at 120° C.

(2) Preparation of Polyimide Resin Solution (Precursor of PolyimideResin)

24.20 g (0.076 moles) of 2,2′-bis(trifluoromethyl)benzidine (TFMB), 1.85g (0.017 moles) of p-phenylenediamine (PDA), 2.36 g (0.008 moles) of1,3-bis(4-aminophenoxy)benzene (TPE-R) and 244.37 g ofN-methyl-2-pyrrolidone (NMP) were placed in a three-necked bottle. Aftercomplete dissolution with stirring at 30° C., 41.75 g (0.091 moles) ofp-phenylenebis(trimellitate anhydride) (TAHQ) and 2.83 g (0.005 moles)of 4,4′-(4,4′-isopropyldiphenoxy)bis(phthalic anhydride) (PBADA) wereadded to the above mixture. Then, the mixture was stirred continuouslyand reacted at 25° C. for 24 hours to obtain the polyimide resinsolution.

(3) Preparation of Mixture of Resin Composition A3

25 g of butanone was added to 10 g of polybutadiene (the number-averagemolecular weight=8600) (which was bought from Cray Valley, Inc.,catalogue number Ricon 134) and 2.2 g oftetramethyltetravinylcyclotetrasiloxane (which was bought from AlfaAesar, catalogue number T22A066) to form a mixture of polybutadieneresin. Then, 6.5 g of the above mixture of polybutadiene resin was addedto 50 g of the above polyimide resin solution and 2.5 g of the abovesurface modified SiO₂ to form a mixture of resin composition A3.

(4) Preparation of Cured Product of Resin Composition A3

A three-wheel roller (400 rpm) was used to uniformly disperse the abovemixture of resin composition A3, and then the mixture was subjected to avacuum defoaming process. Then, the mixture of resin composition A3 wascoated on a copper foil and dried at 140° C. for 6 minutes to carry outthe curing process. Then, the mixture of resin composition A3 was heatedat 380° C. for 10 minutes to carry out a cyclization (imidation)process. Then, the copper foil was removed to obtain a cured film of theresin composition A3, and the thickness of the cured film was measured.

Example 4: Resin Composition A4

(1) Surface Modification of Silica (SiO₂)

20 g of SiO₂ (the volume mean diameter is 2-3 μm) and 0.2 g ofvinyltriethoxysilane (which was bought from Shin-Etsu, catalogue numberKBE-1003) were dispersed in 10 g of water (pH=3.5), and were stirred for20 minutes and dried at 120° C.

(2) Preparation of Polyimide Resin Solution (Precursor of PolyimideResin)

24.20 g (0.076 moles) of 2,2′-bis(trifluoromethyl)benzidine (TFMB), 1.85g (0.017 moles) of p-phenylenediamine (PDA), 2.36 g (0.008 moles) of1,3-bis(4-aminophenoxy)benzene (TPE-R) and 244.37 g ofN-methyl-2-pyrrolidone (NMP) were placed in a three-necked bottle. Aftercomplete dissolution with stirring at 30° C., 41.75 g (0.091 moles) ofp-phenylenebis(trimellitate anhydride) (TAHQ) and 2.83 g (0.005 moles)of 4,4′-(4,4′-isopropyldiphenoxy)bis(phthalic anhydride) (PBADA) wereadded to the above mixture. Then, the mixture was stirred continuouslyand reacted at 25° C. for 24 hours to obtain the polyimide resinsolution.

(3) Preparation of Mixture of Resin Composition A4

25 g of butanone was added to 10 g of polybutadiene (the number-averagemolecular weight=1500) (which was bought from Polysciences, Inc.,catalogue number 22395) and 2.2 g oftetramethyltetravinylcyclotetrasiloxane (which was bought from AlfaAesar, catalogue number T22A066) to form a mixture of polybutadieneresin. Then, 0.7 g of the above mixture of polybutadiene resin was addedto 50 g of the above polyimide resin solution and 2.5 g of the abovesurface modified SiO₂ to form a mixture of resin composition A4.

(4) Preparation of Cured Product of Resin Composition A4

A three-wheel roller (400 rpm) was used to uniformly disperse the abovemixture of resin composition A4, and then the mixture was subjected to avacuum defoaming process. Then, the mixture of resin composition A4 wascoated on a copper foil and dried at 140° C. for 6 minutes to carry outthe curing process. Then, the mixture of resin composition A4 was heatedat 380° C. for 10 minutes to carry out a cyclization (imidation)process. Then, the copper foil was removed to obtain a cured film of theresin composition A3, and the thickness of the cured film was measured.

Comparative Example 1: Resin Composition C1

The process was substantially the same as in Example 1, exceptpolybutadiene resin and SiO₂ were not added.

Comparative Example 2: Resin Composition C2

The process was substantially the same as in Example 1, except SiO₂ wasnot added. The process is described in detail below.

(1) Preparation of Mixture of Resin Composition C2

25 g of butanone was added to 10 g of polybutadiene (the number-averagemolecular weight=1500) (which was bought from Polysciences, Inc.,catalogue number 480843) and 2.2 g oftetramethyltetravinylcyclotetrasiloxane (which was bought from AlfaAesar, catalogue number T22A066) to form a mixture of polybutadieneresin. Then, 3.2 g of the above mixture of polybutadiene resin was addedto 50 g of the above polyimide resin solution to form a mixture of resincomposition C2.

(2) Preparation of Cured Product of Resin Composition C2

A three-wheel roller (400 rpm) was used to uniformly disperse the abovemixture of resin composition C2, and then the mixture was subjected to avacuum defoaming process. Then, the mixture of resin composition C2 wascoated on a copper foil and dried at 140° C. for 6 minutes to carry outthe curing process. Then, the mixture of resin composition C2 was heatedat 380° C. for 10 minutes to carry out a cyclization (imidation)process. Then, the copper foil was removed to obtain a cured film of theresin composition C2, and the thickness of the cured film was measured.

Comparative Example 3: Resin Composition C3

The process was substantially the same as in Comparative Example 2,except 6.2 g of the mixture of polybutadiene resin and 50 g of thepolyimide resin solution were added.

Comparative Example 4: Resin Composition C4

The process was substantially the same as in Comparative Example 2,except 9.5 g of the mixture of polybutadiene resin and 50 g of thepolyimide resin solution were added.

Comparative Example 5: Resin Composition C5

The process was substantially the same as in Comparative Example 2,except 12.5 g of the mixture of polybutadiene resin and 50 g of thepolyimide resin solution were added.

Comparative Example 6: Resin Composition C6

The process was substantially the same as in Comparative Example 2,except 16.65 g of the mixture of polybutadiene resin and 50 g of thepolyimide resin solution were added.

Comparative Example 7: Resin Composition C7

The process was substantially the same as in Comparative Example 2,except 50 g of the mixture of polybutadiene resin and 50 g of thepolyimide resin solution were added.

Comparative Example 8: Resin Composition C8

The process was substantially the same as in Comparative Example 2,except the number-average molecular weight of the polybutadiene (whichwas bought from Polysciences, Inc., catalogue number 480843) was 3000,and 6.2 g of the mixture of polybutadiene resin and 50 g of thepolyimide resin solution were added.

Measurement of Dielectric Loss Factor (Df)

Split-post Dielectric Resonator (SPDR), which can be obtained from GenieNetworks, was used to measure the dielectric loss factor. Specifically,the materials having low dielectric loss factor under high-frequencyconditions (PTFE test piece) were used to form a resonance structure.The sample was placed between the two materials so that the resonancesignal was interfered with, and the dielectric properties of the samplewere obtained by inversion calculation. The dielectric loss factors ofthe resin compositions A1-A4 prepared in Examples 1-4 and the resincompositions C1-C8 prepared in Comparative Examples 1-8 were measured bythe method described above. The dielectric loss factors under conditionsof 10 GHz and 38 GHz (Df@10 GHz and Df@38 GHz) were measured.

Measurement of Coefficient of Thermal Expansion (CTE)

TMA (Thermal Mechanical Analyzer) was used to measure the coefficient ofthermal expansion. Specifically, the sample was placed in a heatingfurnace that can be programmed to heat, cool or maintain a constanttemperature. A constant ambient gas (e.g., nitrogen) was introduced intothe heating furnace. Then, a force of 30 mN was applied to the sample,and the changes of expansion or contraction of sample during heating orcooling were recorded. The linear coefficient of thermal expansion ofthe resin compositions A1-A4 prepared in Examples 1-4 and the resincompositions C1-C8 prepared in Comparative Examples 1-8 were measured bythe method described above.

Measurement of Water Absorption Rate

A sample having an area of 10 cm×10 cm was dried for 1 hour in the ovenat a temperature ranging from 105° C. to 110° C., then the sample wasweighed (W₁). The sample was then soaked in distilled water (23° C.) for24 hours. Then, the soaked sample was taken out, placed betweenabsorbent papers, and rolled in a roller three or four times until therewas no obvious water absorption on the surfaces of the absorbent papers.The sample was then weighed again (W₂). The water absorption rate wasobtained by the formula: water absorption rate=(W₂−W₁)/W₁×100%, W₁=theweight before soak, W₂=the weight after soak. The water absorption ratesof the resin compositions A1-A4 prepared in Examples 1-4 and the resincompositions C1-C8 prepared in Comparative Examples 1-8 were measured bythe method described above.

The results of the analysis of the properties of the resin compositionsprepared in the above Examples 1-4 and Comparative Examples 1-8 aresummarized in Table 1.

TABLE 1 polyimide hydrocarbon water resin resin SiO₂ absorption resin(parts by (parts by (parts by thickness Df @10 Df @38 CTE ratecomposition weight) weight) Mn weight) (mm) GHz GHz (ppm/K) (%) A1 10013.0 1500 5.0 0.029 0.0043 0.0029 34.2 <1 A2 100 13.0 3000 5.0 0.0340.0054 0.0045 31 <1 A3 100 13.0 8600 5.0 0.034 0.0051 0.0054 32 <1 A4100 1.4 1500 5.0 0.042 0.0038 * 37 <1 C1 100 0 — 0 0.024 0.0035 0.005220 1.5-2.5 C2 100 6.4 1500 0 0.026 0.0053 0.0038 31.3 <1 C3 100 12.41500 0 0.029 0.0042 0.0035 28.1 <1 C4 100 19.0 1500 0 0.052 0.00440.0064 32 <1 C5 100 25 1500 0 0.055 0.0039 0.0061 35 <1 C6 100 33.3 15000 0.058 0.0043 0.0056 37 <1 C7 100 100 1500 0 0.032 0.0044 0.0078 57.9<1 C8 100 12.4 3000 0 0.024 0.0062 0.006  30.6 <1 * the data is undermeasurement

It can be observed from the results in Table 1 that the addition of thehydrocarbon resin can reduce or maintain the dielectric loss factor ofthe resin composition in the high-frequency section (about 30 GHz toabout 40 GHz). The dielectric loss factor of the resin composition doesnot rapidly increase in a high-frequency environment, and therefore caneffectively reduce the loss of signal transmission.

In addition, the resin composition provided in the embodiments may havea water absorption rate of less than about 1%, and the linearcoefficient of thermal expansion may be maintained below 35 ppm/K. Onthe other hand, hydrocarbon resins having the number-average molecularweight within a specific range have the effect of lowering thedielectric loss factor.

Example 5: Resin Composition B1

(1) Surface Modification of Silica (SiO₂)

20 g of SiO₂ (the volume mean diameter is 2-3 μm) and 0.2 g ofvinyltriethoxysilane (which was bought from Shin-Etsu, catalogue numberKBE-1003) were dispersed in 10 g of water (pH=3.5), and were stirred for20 minutes and dried at 120° C.

(2) Preparation of Polyimide Resin Solution (Precursor of PolyimideResin)

24.20 g (0.076 moles) of 2,2′-bis(trifluoromethyl)benzidine (TFMB), 1.85g (0.017 moles) of p-phenylenediamine (PDA), 2.36 g (0.008 moles) of1,3-bis(4-aminophenoxy)benzene (TPE-R) and 244.37 g ofN-methyl-2-pyrrolidone (NMP) were placed in a three-necked bottle. Aftercomplete dissolution with stirring at 30° C., 41.75 g (0.091 moles) ofp-phenylenebis(trimellitate anhydride) (TAHQ) and 2.83 g (0.005 moles)of 4,4′-(4,4′-isopropyldiphenoxy)bis(phthalic anhydride) (PBADA) wereadded to the above mixture. Then, the mixture was stirred continuouslyand reacted at 25° C. for 24 hours to obtain the polyimide resinsolution.

(3) Preparation of Mixture of Resin Composition B1

A few of 1,2-dimethoxyethane (DME) was added to 1.6 g of PTFE resins(the volume mean diameter is 3-4 μm) (which were bought from DAIKIN,catalogue number L-5F) to swell the PTFE resins. Then, 50 g of polyimideresin solution, 20 g of 1,2-dimethoxyethane and 1.85 g of the abovesurface modified SiO₂ were added to the swelled PTFE resins to form amixture of resin composition B1.

(4) Preparation of Cured Product of Resin Composition B1

A three-wheel roller (400 rpm) was used to uniformly disperse the abovemixture of resin composition B1, and then the mixture was subjected to avacuum defoaming process. Then, the mixture of resin composition B1 wascoated on a copper foil and dried at 140° C. for 6 minutes to carry outthe curing process. Then, the mixture of resin composition B1 was heatedat 380° C. for 10 minutes to carry out a cyclization (imidation)process. Then, the copper foil was removed to obtain a cured film of theresin composition B1, and the thickness of the cured film was measured.

Example 6: Resin Composition B2

The process was substantially the same as in Example 4, except 3.3 g ofthe PTFE resin (the volume mean diameter is 3-4 μm) (which were boughtfrom DAIKIN, catalogue number L-5F), 1.95 g of surface modified SiO₂,and 50 g of the polyimide resin solution were added.

Example 7: Resin Composition B3

The process was substantially the same as in Example 4, except 6 g ofthe PTFE resin (the volume mean diameter is 3-4 μm) (which were boughtfrom DAIKIN, catalogue number L-5F), 2.0 g of surface modified SiO₂, and50 g of the polyimide resin solution were added.

Example 8: Resin Composition B4

The process was substantially the same as in Example 4, except 9.2 g ofthe PTFE resin (the volume mean diameter is 3-4 μm) (which were boughtfrom DAIKIN, catalogue number L-5F), 2.15 g of SiO₂, and 50 g of thepolyimide resin solution were added.

Example 9: Resin Composition B5

The process was substantially the same as in Example 4, except 13.05 gof the PTFE resin (the volume mean diameter is 3-4 μm) (which werebought from DAIKIN, catalogue number L-5F), 2.3 g of SiO₂, and 50 g ofthe polyimide resin solution were added.

Example 10: Resin Composition B6

(1) Surface Modification of Silica (SiO₂)

20 g of SiO₂ (the volume mean diameter is 0.5 μm) and 0.2 g ofvinyltriethoxysilane (which was bought from Shin-Etsu, catalogue numberKBE-1003) were dispersed in 10 g of water (pH=3.5), and were stirred for20 minutes and dried at 120° C.

(2) Preparation of Polyimide Resin Solution (Precursor of PolyimideResin)

24.20 g (0.076 moles) of 2,2′-bis(trifluoromethyl)benzidine (TFMB), 1.85g (0.017 moles) of p-phenylenediamine (PDA), 2.36 g (0.008 moles) of1,3-bis(4-aminophenoxy)benzene (TPE-R) and 244.37 g ofN-methyl-2-pyrrolidone (NMP) were placed in a three-necked bottle. Aftercomplete dissolution with stirring at 30° C., 41.75 g (0.091 moles) ofp-phenylenebis(trimellitate anhydride) (TAHQ) and 2.83 g (0.005 moles)of 4,4′-(4,4′-isopropyldiphenoxy)bis(phthalic anhydride) (PBADA) wereadded to the above mixture. Then, the mixture was stirred continuouslyand reacted at 25° C. for 24 hours to obtain the polyimide resinsolution.

(3) Preparation of Mixture of Resin Composition B6

A few of 1,2-dimethoxyethane (DME) was added to 17.5 g of PTFE resins(3-4 μm) (which were bought from DAIKIN, catalogue number L-5F) to swellthe PTFE resins. Then, 50 g of polyimide resin solution, 20 g of1,2-dimethoxyethane and 2.45 g of the above surface modified SiO₂ wereadded to the swelled PTFE resins to form a mixture of resin compositionB6.

(4) Preparation of Cured Product of Resin Composition B6

A three-wheel roller (400 rpm) was used to uniformly disperse the abovemixture of resin composition B6, and then the mixture was subjected to avacuum defoaming process. Then, the mixture of resin composition B6 wascoated on a copper foil and dried at 140° C. for 6 minutes to carry outthe curing process. Then, the mixture of resin composition B6 was heatedat 380° C. for 10 minutes to carry out a cyclization (imidation)process. Then, the copper foil was removed to obtain a cured film of theresin composition B6, and the thickness of the cured film was measured.

Example 11: Resin Composition B7

The process was substantially the same as in Example 9, except thevolume mean diameter of SiO₂ is 3 μm.

Example 12: Resin Composition B8

The process was substantially the same as in Example 9, except thevolume mean diameter of SiO₂ is 11 μm.

Example 13: Resin Composition B9

The process was substantially the same as in Example 9, except thevolume mean diameter of SiO₂ is 25 μm.

Comparative Example 9: Resin Composition C9

The process was substantially the same as in Example 4, except the PTFEresins and SiO₂ were not added.

Comparative Example 10: Resin Composition C10

The process was substantially the same as in Example 4, except SiO₂ wasnot added. The process is described in detail below.

(1) Preparation of Mixture of Resin Composition C10

A few of 1,2-dimethoxyethane (DME) was added to 16.5 g of PTFE resins(the volume mean diameter is 3-4 μm) (which were bought from DAIKIN,catalogue number L-5F) to swell the PTFE resins. Then, 50 g of polyimideresin solution and 20 g of 1,2-dimethoxyethane were added to the swelledPTFE resins to form a mixture of resin composition C10.

(2) Preparation of Cured Product of Resin Composition C10

A three-wheel roller (400 rpm) was used to uniformly disperse the abovemixture of resin composition C10, and then the mixture was subjected toa vacuum defoaming process. Then, the mixture of resin composition C10was coated on a copper foil and dried at 140° C. for 6 minutes to carryout the curing process. Then, the mixture of resin composition C10 washeated at 380° C. for 10 minutes to carry out a cyclization (imidation)process. Then, the copper foil was removed to obtain a cured film of theresin composition C10, and the thickness of the cured film was measured.

The dielectric loss factors under conditions of 10 GHz and 38 GHz, thelinear coefficient of thermal expansion and the water absorption rate ofthe resin compositions B1-B7 prepared in Examples 5-13 and the resincompositions C9-C10 prepared in Comparative Examples 9-10 were measured.The method for measurement of the dielectric loss factor, linearcoefficient of thermal expansion and water absorption rate were the sameas described above.

The results of the analysis of the properties of the resin compositionsprepared in the above Examples 5-13 and Comparative Examples 9-10 aresummarized in Table 2.

TABLE 2 polyimide fluorinated water resin polymer resin SiO₂ SiO₂absorption resin (parts by (parts by (parts by particle size thicknessDf @10 Df @38 CTE rate composition weight) weight) weight) (μm) (mm) GHzGHz (ppm/K) (%) B1 100 3.2 3.7 3 0.029 0.0038 0.0055 30 0.84 B2 100 6.63.9 3 0.0315 0.0043 0.0043 29 0.76 B3 100 12 4.0 3 0.0315 0.0034 0.004932 0.63 B4 100 18.4 4.3 3 0.035 0.0040 0.0044 37 0.52 B5 100 26.1 4.6 30.0365 0.0036 0.0046 40 0.81 B6 100 35 4.9 0.5 0.0435 0.0034 0.0037 39.90.46 B7 100 35 4.9 3 0.043 0.0035 0.0024 45.2 0.48 B8 100 35 4.9 110.038 0.0034 0.0045 38 0.29 B9 100 35 4.9 25 0.041 0.0038 0.0051 37 0.77C9 100 0 0 — 0.027 0.0035 0.0052 20 1.5-2.5 C10 100 33 0 — 0.0365 0.00370.0043 41 0.6 

It can be observed from the results in Table 2 that the addition of thefluorinated polymer resin can reduce or maintain the dielectric lossfactor of the resin composition in the high-frequency section. Thedielectric loss factor of the resin composition does not rapidlyincrease in a high-frequency environment, and therefore can effectivelyreduce the loss of signal transmission.

To summarize the above, in accordance with some embodiments of thepresent disclosure, the resin composition including polyimide resins andfluorinated polymer resins or hydrocarbon resins is provided. Thefluorinated polymer resin and the hydrocarbon resin are added so thatthe resin composition can still maintain good dielectric properties in ahigh-frequency environment and the loss of signal transmission can beeffectively decreased. Therefore, when the elements made of such resincomposition (e.g., a substrate, a printed circuit board, or the like)are applied to a signal transmission device, the rate of high-frequencytransmission and the integrity of the transmission signal of the devicecan be improved.

Although some embodiments of the present disclosure and their advantageshave been described in detail, it should be understood that variouschanges, substitutions and alterations can be made herein withoutdeparting from the spirit and scope of the disclosure as defined by theappended claims. For example, it will be readily understood by one ofordinary skill in the art that many of the features, functions,processes, and materials described herein may be varied while remainingwithin the scope of the present disclosure. Moreover, the scope of thepresent application is not intended to be limited to the particularembodiments of the process, machine, manufacture, composition of matter,means, methods and steps described in the specification. As one ofordinary skill in the art will readily appreciate from the presentdisclosure, processes, machines, manufacture, compositions of matter,means, methods, or steps, presently existing or later to be developed,that perform substantially the same function or achieve substantiallythe same result as the corresponding embodiments described herein may beutilized according to the present disclosure. Accordingly, the appendedclaims are intended to include within their scope such processes,machines, manufacture, compositions of matter, means, methods, or steps.

What is claimed is:
 1. A resin composition, comprising: a polyimideresin; a hydrocarbon resin; and a silica that is modified by a surfacemodifier, wherein the content of the hydrocarbon resin is in a rangefrom 1 to 13 parts by weight based on 100 parts by weight of thepolyimide resin, and the content of the silica is in a range from 1 to10 parts by weight based on 100 parts by weight of the polyimide resin,and wherein the polyimide resin is copolymerized by the followingcomponents: (a) at least two dianhydride monomers, one of thedianhydride monomers is p-phenylenebis(trimellitate anhydride) and itscontent accounts for 80-95% of the total moles of the dianhydridemonomers; and the other dianhydride monomers are selected from a groupconsisting of 4,4′-(hexafluoroisopropylidene)-diphthalic anhydride, and4,4′-(4,4′-isopropyldiphenoxy)bis(phthalic anhydride); and (b) at leasttwo diamine monomers, wherein one of the diamine monomers is2,2′-bis(trifluoromethyl)benzidine and its content accounts for 70% to90% of total moles of the diamine monomers; and the other diaminemonomers are selected from a group consisting of 4,4′-diaminodiphenylether, 4,4′-diaminodiphenylmethane,2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4′-diaminodiphenyl-sulfone,1,3-bis(4-aminophenoxy)benzene, 4,4′-diaminobenzanilide,p-phenylenediamine, 4,4′-diamino-2,2′-dimethyl-1,1′-biphenyl,2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and4,4′-diamino octafluorobiphenyl,2,2-bis(3-amino-4-tolyl)hexafluoropropane, and2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and its contentaccounts for 10% to 30% of the total moles of the diamine monomers;wherein a ratio of the total moles of the dianhydride monomers to thetotal moles of the diamine monomers is in a range from 0.85 to 1.15. 2.The resin composition as claimed in claim 1, wherein the otherdianhydride monomers comprise4,4′-(hexafluoroisopropylidene)bis-phthalic anhydride and its contentaccounts for not more than 15% of the total moles of the dianhydridemonomers.
 3. The resin composition as claimed in claim 1, wherein thesurface modifier comprises vinyltriethoxysilane, propyltrimethoxysilane,propyltriethoxysilane, isobutyltrimethoxysilane,isobutyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane,octadecyltrimethoxysilane, octadecylethoxysilane,N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, aminoethyl aminopropyl trimethoxysilane,aminoethyl aminopropyl triethoxysilane,3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane,or a combination thereof.
 4. The resin composition as claimed in claim1, wherein a volume mean diameter of the silica is in a range from 0.5μm to 25 μm.
 5. The resin composition as claimed in claim 1, wherein thecontent of the surface modifier is in a range from 0.1 to 5 parts byweight based on 100 parts by weight of the silica.
 6. The resincomposition as claimed in claim 1, wherein the hydrocarbon resincomprises polybutadiene, polybutadiene-styrene mixture, polyisoprene,cyclic olefin copolymer, butadiene-styrene-divinylbenzene copolymer, ora combination thereof.